Sulfonated aromatic derivatives



Patented Dec. 7, 1948 UNITED STATES PATENT' ol-"rica SULFONATED AROMATIC DERIVATIVES John a. Caldwell, Kingsport, 'lenn., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 5, 1945, Serial No. 597,707

This invention relates to the preparation of a new class of chemical compounds useful for a wide variety of purposes, especially as surfaceactive agents, emulsifying agents, additives for lubricating oils and constituents for textile lubricating fluids. The invention relates more particularly to the preparation of new types of aromatic sulfonic acids which may be described as sulfonated fatty acid esters of aryl-alkyl hy- For a considerable period of time there has existed a need for compounds of the type in question which would contain three functional groups in addition to the sulfonated aromaticnucleus in order to provide a greater range of solubility in various solvents than is possessed by the aromatic sulfonic acids of the prior art. So far as I am aware, until the advance of the present invention, no such compounds have been prepared or described in the literature.

The present invention has as its principal object to prepare fatty acid derivatives containing aromatic sulfonic acid groups. A further object is to provide high molecular weight derivatives containing an aromatic sulfonic acid group in combination with ether and ester groups. A still further object is to provide a new class of chemical compounds which may be identified as sulfonated fatty acid esters of aryl-alkyl hydroxy ethers. Other objects will appear hereinafter.

These objects are accomplished by the following invention which comprises preparing the compounds in question by the followin sequence of steps:

(a) An aryl-hydroxy alkyl ether is esterified with a fatty acid to give an ether-ester having the structure wherein X is an aromatic nucleus, Y is an alkylene group containing from 2 to 6 .carbon atoms, R isv an alkyl or alkylen'e group containing 9 to 24 carbonatoms, and n is a whole number from 1 to 3.

(b) The ether-ester is then sulfonated with a '3 Claims. (Cl. 26H01) suitable sulfonating agent to give a monoor di-sulfonic acid having the structure (nsoa -x-o-w-on-co-n wherein X, Y, R and a have the significance indicated above.

(c) The sulfonic acid of (b) is then neutralized with a suitable alkali metal hydroxide or an amine.

While I prefer the above procedure, other methods of synthesis may beemployed. For example, a sodium phenate may be reacted with a chloroester to give the intermediate shown in (a) above thus:

Sulfonating agents that may be used in the process include concentrated sulfuric acid, fuming sulfuric acid (10-60% S03), and chlorosulfonic acid. w

,The derivatives thus contemplated by my invention are salts of aromatic sulfonic acids containing within their molecular structure ether groups, ester groups, and hydrocarbon radicals containing 10 or more carbon atoms, and maybe represented by the graphic formula wherein M-is an alkali metal or non-aromtaic amine, X is an aromatic nucleus which may or may not contain other substituents, Y is an alkylene group having a straight or branched chain and containing from 2 to 6 carbon atoms, R is an alkyl or alkylene group containing 9 to 24 carb'on atoms and may contain other substituents such as halogen, ether linkages, etc., and may be a straight or branched chain or a cyclic radical, m is 1-2 and n is 1-3.

In further explanation of the identity of the various components of which my novel compounds are composed, it may be said that M is a positive ion derived from an alkali metal such assodium, potassium, or lithium. Alternatively, M may be a positive ion derived from an amine such "as ethyl amine, n-butyl amine, cyclohexyl amine, ethylene diamine, etc. A particularly useful class of amines is the alkylol'amines as represented by monoethanol amine, diethanol amine, 3-hydroxy-1-butyl amine, 1,3-diamino-2- hydroxy propane, 2-amino-1-butanol, etc. Although it is preferred to use the salts in most cases, the scope of the invention also includes the preparation and use of the free sulfonic acid.

X is anaromatic nucleus such as benzene, naphthalene, anthracene, or retene. It may contain with monoethanol amine.

other substituent groups such as alkyl groups, alkoxy groups, halogen. or aryl groups. It should not contain carborwl groups or amino groups.

Y may be an alkylene group as exemplified by R is an aliphatic or cycloaiiphatic radical de? I rived from a fatty acid containing 10-25 carbon atoms. Suitable acids are lauric acid, palmitic acid, margaric acid, myrlstic acid, stearic acid, naphthenic acids, etc. Fatty acids containing double bonds or substituent groups may be employed, as exemplified by oleic acid, elaidic acid and 9-phenyl stearic acid. Mixed fatty acids, such as those derived from the saponiflcatlon of naturally occurring frts and oils, are particularly suitable. Examples of mixed fatty acids are: mixed olive oil fatty acids, mixed tallow fatty acids, and mixed whale oil fatty acids.

In the following examples and description I have set forth several of the preferred embodiments of my invention. but they are included merely for purposes of illustration and not as a limitation thereof.

Example 1 Beta-phenoxy ethanol (1 mol, 140 g.) is esterifled with 1 mol (282 g.) oleic acid to give the compound:

The ester is dissolved in 300 cc. ethylene dichloride and cooled to l-15 C. While maintaining this temperature, a mixture of 100 g. fuming (60%) sulfuric acid and 100 g. (98%) sulfuric acid is slowly added. The solution is then allowed to warm up to 20-30 C. and is stirred for one hour. It is then poured into chilled 20% sodium chloride solution and stirred to wash out free sulfuric acid. The oily layer is separated off and neutralized After evaporation of the ethylene dichloride under vacuum at Bil-90 C. the monoethanol amine sulfonic acid salt is left as a soft wax. It gives a clear solution in water and is not precipitated by calcium or magnesium salts, showing that it is a true sulfonic acid. It has the formula:

substituted aromatic sulfonic acid is characterized by its solubility in a wide range of organic liquids, as represented by the lower alcohols, ketones such as methyl-butyl ketone, amyl acetate, ethylene dichloride, ether, and many others.

Example 2 One mol of meta-phenoxy ethanol is esterified with oleic acid. The ether-ester is dissolved in r 200 cc. ethylene dichloride and heated to 50-60 C. With good agitation, 116 g. (1 mol) chlorosulfonic acid dissolved in- 70 cc. ethylene dichloride is slowly added. Air is passed through the solution until all hydrogen chloride is re moved. The sulfonic acid is neutralized with diethylcyclohexyl amine. The'salt is a soft was that has the structure Example 3 Beta-tolyloxy'isopropanol is esterifled with a naphthenic acid fraction having an equivalent weight of 260-270. The ester is sulfonated with a molar proportion of chlorosulfonic acid as described in Example 2 above. The dibutyl amine salt is prepared. It has the structure O-CHr-CH-O-C 0-11 (0435) :NHr- 8 0s R is the naphthenyl radical. This compound is valuable as a surface-active and emulsifying agent. It is soluble in a wide range of organic liquids, and aqueous dispersions can be prepared readily by dissolving the sulfonic acid amine salt and many others, whileat the same time tending to be soluble in water. v

The compounds of my invention find their most useful application as surface-active agents. For example, the. aromatic sulfonic acids and salts thereof as prepared by the processes described above, are valuable emulsifying agents useful for the preparation of aqueous emulsions or dispersions of mineral oils, vegetable oils, fats, waxes, and the like. My novel compounds are especially valuable for preparing emulsions and dispersions employed in treating textile materials in general and particularly in treating those composed of or containing cellulose organic acid esters such as cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate and related materials. Salts formed by neutralizing the aromatic sulfonic The compounds of the invention can also be employed to disperse many types of organic liquids in water to give emulsions. An outstanding property of the aromatic sultonic acids and salts is their miscibility with practically all types of organic liquids. As indicated above, this property of solubility of the compounds in many types of diflerent organic solvents apparently arises from the diversity of functional groups present. The compounds of the invention are miscible with or soluble in most types of alcohols, ketones, ethers, esters, hydrocarbons and halogenated hydrocarbons. Emulsions of these various solvents can be formed readily by dissolving the sulionic acid salts in the solvent, and pouring the solution into water.

In addition to the above uses the compounds of the invention are of value as modifying gents for lubricating oils. For example, the aromatic sulfonic acids or their salts may be added in amounts of 0.1 to 1% to extreme pressure lubricants, in order to improve fllm strength. Many other properties make these compounds unique and valuable additions to the known sulionic acids and derivatives thereof.

What I claim is: l 1. -As a new chemical compound a sulfonated fatty acid ester 01 an aryl hydroxyalkyl ether having the graphic formula:

(MBOilm-X-O-(Y-Oh-CO-R wherein M is a positive ion, 8 is a mononuclear aryl group of the benzene series..Y is an alkylene groupcontsiningfi-dcarbon'atoms andRiso-n aliphatic radicalselected iron the group conasoavso sisting of the straight chain aliphatic and cycloaliphatic radicals derived from fatty acids containing 10-25 carbon atoms, m is 1-2 and n is 1-3.

fatty acid ester of an aryl hydroxyalkyl ether having the graphic formula:

Qocm r-o-co-oana 0am; I

wherein M is a positive ion. m'is 1-2 and n is 1-3.

'3. As a new chemical compound.

Ho-cna-Nra-so o-otm-o-o o-oana JOHN R; oa mwna. REFERENCES CITED The following references flle of this patent:

UNITED STATES PATENTS Groggins, 1938, McGraw-Hill 237-43, 248-60. (Copy Division 68.)

2. As a new chemical compound a sulionated areoirecordinthe.

ca. mea ass-4, 

